Method fob solubilizing insoluble



Patented July 19, an

METHOD FOR SOLUBILIZING INSOLUBLE I GELATINIZED OILS Max Kronstein, New York, N. Y.

No Drawing. Application May is, 1947, Serial No. 748,685

15 Claims.

1 This invention relates to the solubilizing oi insoluble, gelatinized fixed oils, such as vegetable, animal, or synthetic oils or mixtures oi. derivatives of such oils or of such oils with other materials and has particular relation to a process of solubilizing such insoluble gelatinized materials so that they can be made useful in oleoor oleo-resinous compounds, in varnish, lacquer, coating, extrusion, covering, impregnation, insulation compounds or the like. The present application is a continuation-in-part of my co-' pending allowed application Serial No. 496,262 (now abandoned).

It is known that the most desirable bases for use in preparing coating compositions are those which produce coatings having a minimum degree oi swelling. The swelling capacity of a material is characterized by the fact that the swelling is connected with an increase in volume and the deswelling, i. e., shrinking, is connected with a decrease in volume. Thus it is general practice in the coating art to avoid the use of varnishes, oils, lacquers, or similar compounds which are in a swollen condition. (Fixed oils are defined in Hackh's Chemical Dictionary, second edition, 1937, as those oils which consist of the fatty substances of vegetable and animal organism and contain the esters of fatty acids.) For example, fixed oils which can be readily transformed as by polymerization, or by the application of heat, by distillation or by chemical action into a paritially insoluble condition and having some swelling ability, are generally used in a non-gelatinous condition. Thus gelatinized fixed oils have heretofore been of little use in the coating arts.

It has been observed that such materials which are used in a swollen condition, as for instance highly polymerized fixed oils, undergo shrinking while drying and that during the drying or in the shrunken condition, such materials lose most of their ability to swell, probably by virtue of oxidation, polymerization, or other chemical action. One possible explanation is that the components of such materials are apparently connected to each other in a special manner and in a different manner than are the molecules oi other materials which are readily soluble in the usual thinners or varnish solvents.

An object of the present invention is to provide a process for treating insoluble, gelatinous, swollen oils so that they are capable of being applied by coating or covering methods, as by brushing, spraying, dipping, or extruding, and can further be compounded without the necessity oi being returned to a non-swelling condition.

Another object oi the invention is to provide a process for the preparation of a stable, soluble oil base composition having a high shrinkage capacity-when dried from a state of solution.

A further object of the invention is to provide a process for solubilizing a swelled, insoluble, gelatinous fixed oil base composition.

Still another object of the invention is to provide a process for modifying the coating characteristics of fixed oils so as to bring them into a swelling or swollen condition where they can be readily worked up or dissolved into a liquid state, and in which condition they can be stored indefinitely and then can be used directly and can be readily worked up or dissolved into a liquid state, and in which condition they can be stored indefinitely and then can be used directly and can be readily diluted for use as a coating composition.

A still further object of the invention is to provide a fixed oil base coating composition which will have desirable coating or covering characteristics, such as a high degree of elasticity, resistance to hardening, aging, changes in temperature and changes in humidity, and which can be modified by compounding with resins, asphalts, phenolic resins, alkyd resins and other synthetic resinous materials, copal gums, and the like.

Still another object of the invention is to provide a process for solubilizing gelatinized oleo compounds in the presence of natural gums, resins, asphalts and other natural materials thereby obtaining useful compounds of solubilized gels with the natural material.

Still another object of the invention is to provide a process for solubilizing those insoluble fixed oils which are incapable of forming coherent film-like substances, so that they may be used subsequently as film-forming coatings.

Still another object is to provide a process for solubilizing gelatinized oleo compounds in the presence of synthetic resinous compounds such as-phenolic resins or alkyd resins thereby obtaining useful compounds of such solubilized gels with synthetic resinous materials.

Still another object is to provide a process for solubilizing gelatinized oleo compounds in such manner that the products can be dissolved in solvents and plasticizers for use in lacquers, cellulose derivatives and vinyl compounds, and can be dissolved readily in polymerizable liquids or solutions, such as styrene or the like to form stable solutions.

Another object 01 the invention is to provide a process for increasing the swelling capacity of swollen or swelling oils, to such an extent that they can'be worked up in the usual thinners and varnish solvents.

These and other objects of the invention will be readily understood by reference to the following description:

I have discovered that metal soap-like reaction products, preferably formed by reacting a fixed oil, a petroleumacid, a rosin acid, or mix; ture thereof with a compound of a metal capable of reaction with such 'oils, fatty acids, resin acids, naphthenic acids or other organic com- .'pounds to form a corresponding oil soluble metal by melting and compounding therewith certain metallic soap-like reaction products by subjecting the mixture to a melting temperature such that substantially the entire mass of the resulting composition is melted into the liquid stage thereby forming a soluble oil which is capable of forming a, stable solution.

I have also discovered that the above-discovered process may be practiced with success by utilizing a metallic soap-like reaction product which is at least partially soluble in an oil and which is in a liquid state at the melting temperature of the above-set forth process. 1

According to my invention, fixed oils, which are insoluble or at least partially insoluble, may be solubilized by melting and reacting therewith, at a temperature below the decomposition temperature of the resulting compound, a metal soap-like reaction product.

By fixed oil I mean to include any oil which consists of the fatty substances of vegetable or animal organisms containing an ester of a fatty acid; -or any fatty acids or their derivatives; or any synthetically produced 011 containing an ester of a fatty acid; or any synthetically produced fatty acid oil-like ester.

By insoluble I mean to include the characterization of any compound which is incapable of dissolving in a liquid to form a stable homogeneous mixture.

By gelatinized I mean to include any fixed oil which is at least partially insoluble and which is capable of increasing its volume when contacted by a solvent (swelling capacity) In addition, I mean to include not only those gelatinized fixed oils which are film-forming but also those which are not capable of forming a film.

By solubilizing I mean to include the treatment of any insoluble or at least partially insoluble material to the extent that it will be capable of mixing with a liquid to form a stable, homogeneous solution.

By metal soap-like reaction product I mean to include any alkali, alkaline-earth, or heavy metal compound of a complex organic acid or ester thereof, which is at least partially soluble in a fixed oil.

By stable I mean to include any compound or solution which will remain in a balanced condition of miscibility which is not readily destroyed.

It is possible that the metal soap-like reaction products of the present invention may influence the degree of swelling without producing a. chemical reaction. In preparing a contact substance; that is, a metal soap-like reaction product in accordance with the present invention oils or their acids or mixtures of such materials are treated in the presence of compounds such as metallic peroxides, acetates, oxides, hydroxides, carbonates, borates, or other inorganic or organic metal salts, at a temperature which is suf- I swa iiciently elevated to v cause a reaction to take place between the oil and the metal compound so as to form the "corresponding metal soap-like reaction product- The resulting reaction product is clearly distinguished from other chemical substances by its ability to raise the swelling capacity of insoluble, gelatinous swollen or swelling oils, when compounded therewith, to such an extent that the resulting composition can be worked up in the usual thinners or varnish solvents. It will be understood that the insoluble, gelatinous swollen or swelling oils which are treated with the metal soap-like contact substance in accordance with the present in vention may result from heating, distillation,

polymerization, oxidation, condensation such as a the phthalic acid reaction, the action of sulphur, or of accelerators such as sulphur chlorides, boron fluorides, tin tetrachlorides, or other chemical action, or from various combinations of such reactions.

The exact nature of the compounding of the contact substance with the insoluble, gelatinous swelling or swollen fixed oil is not clearly understood. However, it is believed that the compounding results in the formation of a solution or in the formation of a condition of unlimited swelling. It has been found that alkali, alkaliearth, and heavy metals selected from eachof the groups of the periodical system may be utilized to form metallic soap-like reaction prod- 'ucts which may be used successfully as contact substances in practicing the present invention.

In the practice of the present process the relation between the insoluble gelatinized, swelling oil and the contact substance depends in part upon the degree of swelling of the insoluble, gelatinized oil. If the gelatinized oil is in condition to be readily swelled, only a minimum amount of contact substance is required; whereas a greater amount is necessary if the gelatinized oil is in a condition which may not be readily swelled. Thus, it has been found that fresh gelatinized oils require a smaller .proportion of contact substance than is required for gelatinized oils which are in an .aged condition. Likewise, certain oils, which have been highly gelatinized by continued heating, distillation or vacuum treatment, require an increased amount of contact substance. Oils which have been altered or modified by the removal of the nongelatinized components also require an increased amount of contact substance.

While it has been found that an excess amount of contact substance may be used for obtaining certain desired characteristics, the proportions set forth in the following examples are preferred.

In a further embodiment of the invention, it has been found that the process of liquifying the gelatinous compound with a metal soap-like reaction product may be promoted or accelerated by adding a non-gelatinous oil or other mate,- rial which is liquid at the temperature of the reaction and has the properties of acting as a solvent for the metal soap-like reaction product and ass. sweller for the gelatinous compound.

In another embodiment of the invention, it has been found that .free acids contained in the soap-like reaction products may be removed or neutralized by heating them with borates, such as manganese or calcium borate and that such treatment does not interfere with the nature of assume It will be seen from the following examples that they relate to a preferred process for the preparation of the metallic soap-like reaction products which are used as a contact substance for solubilizing the swelled, insoluble gelatinous oil.

Certain examples relate to a preferred process for preparing swollen, insoluble, gelatinous fixed oils, although it will be understood that any swollen, insoluble, gelatinous fixed oils resulting from other processes may be used.

Other examples relate to a preferred process for solubilizing a swollen, insoluble, gelatinous oil or oil base, by treating the gelatinous oil with contact substances, wherein such process is performed in the presence of materials, which are neither a component part of the gelatine nor a component part of the contact substance, nor a non-gelatinous form of a gelatinous oil material.

The following working examples illustrate the preferred conditions and compounds which may be utilized in practicing my invention but it will be understood that the scope of the invention is not confined thereto:

PREPARATION or THE METALLIC SOAP-LIKE REACTION PRODUCT CoNTAcT SUBSTANCE I. Fixed oils A. Vegetable oils.

1. Drying oils.

Example 1 About 93 parts by weight of linseed oil was heated in a reaction kettle. When the heated oil attained a temperature ranging from 150 to 200 0., about 1.5 parts by weight of cobalt acetate was added slowly, with stirring, to the kettle. It was noted that the linseed oil raised up in the kettle during the reaction and during the escaping of the lay-products, which probably included acetic acid, as the reaction product was eventually freed from the acetate used. Heating of the reaction product, which was a soluble cobalt linseed oil reaction product, was then continued until the temperature thereof was above 200" C. and the temperature was so maintained until the reaction was completed.

Example 111 In place of the cobalt acetate used in Example 1, about 2.5 parts of iron acetate or corresponding quantities of cobalt or iron oxide were used as the compound capable of reacting with the oil to form the corresponding metal soap-like reaction product.

Example 2 Similarly as in Example 1 above, in the following examples drying oils and metal compounds were reacted to form metal son-alike reaction products. It was found preferable to use about 1 by weight of metal compounds to parts of oil. The temperatures used were substantially those used in Example 1.

(a) 93 parts or linseed oil and 4 parts lead acetate.

(b) 93 parts of soyabcan oil and 4.2

parts cobalt acetate.

(0) 93 parts of perilla oil and 6.2

parts cupric acetate.

(d) 93 parts of linseed oil and 5.4

aluminum acetate.

(f) 93 parts of linseed parts, of iron oxide.

(0) 93 parts of perilla oil and 11.5

parts zinc sulphate.

(h) 93 parts of perilla oil and 9.3

parts silver nitrate, (A surplus of the silver nitrate salt remained after coolin as a solid at the bottom of e container.) (h) 93 parts linseed oil and 13 parts nO (55% 2. Sena-drying and non-drying vegetable (i) 93 parts cashew nut shell liquid and 4.8 parts cobalt acetate. About 13% of the liquid evaporated during the treatment. (I) 93 parts of cottonseed oil and 7.7 parts cobaltous nitrate. B. Animal oils.

formiate. D. Oil distillation.

(p) 93 parts of distillate from cottonseed oil and 6 parts of cobalt acetate.

(q) 31 parts of distillate from perilla oil, 62 arts of additional perilla 01 and 4.8 parts of cobalt acetate.

E. Fatty acids.

(1') 93 parts of oleic acid and 20 parts of zinc benzoate. (Heated up to about C. at which temperature much of the benzoic acid escaped.)

(s) 93 parts of oleic acid and 20 parts of lead hydroxide. (Heated up to about 185 C.)

(t) 93 parts of linoleic acid and 2.15

parts basic bismuth acetate.

(u) 93 parts linoleic acid and 2.4

parts chromium carbonate.

(1:) 93 parts linoleic acid and 2.8

parts manganese acetate.

(10) 93 parts rosin oil and 2.35 parts 50 parts linseed oil and 2.5 parts cobalt acetate. (NJ) 93 parts linseed oil,

' 2 parts cobalt acetate and 1 part iron oxide. 77.5 parts bodied linseed oil, 15.5 parts oleic acid and 1.6 parts cobalt acetate. 77.5 parts heat-bodied linseed oil, 15.5 parts rosin acid and 2 parts cobalt acetate. (ee) 47 parts linseed oil, 46 parts rosin oil and 2 parts cobalt acetate. 70 parts linseed oil, 23 arts stearic acid and 2.3mt parts basic bismuth ace to al-is linseed oil, 23 parts naplfihenic acid and 2.4 parts co t acetate.

II. Rosin acids.

PREPARATION or rm: Insomsrr Swsnmo Gnurmous n.

Example 3 Raw linseed oil was heated in a reaction kettle to a temperature ranging from about 285 to 290 C. for the promotion of the polymerization, air was directed through the linseed oil as a contact agent, although oxygen may also be directed through the oil for the same purpose. The reaction is generally completed by the heat generated by the reaction, which ordinarily causes a 20 C. rise in temperature. If the self-heating does not occur readily, the reaction kettle should be further heated until a temperature has been reached where the final gelatinizing effect occurs. This gelatinizing efiect can be readily recognized by the fact that the oil loses its liquid characteristics and turns gelatinous. Heating was discontinued assoon as the gelatinizing effect had occurred. Upon cooling, the swelled insoluble gelatinous, viscous oil resulting from the heating, further solidified into a viscous elastic compound, which could be stretched; i. e., extended, and which exhibited resistance to being torn apart.

In place of the raw linseed oil, a pretreated, preheated, and bodied linseed oil, and a mixture of such oils, plus a drier or resin, were also used.

Example 4 The process of the preceding example was followed to obtain gelatinization and insolubilization of the following oils:

Soy bean oil,

Perilla oil.

A mixture of 4 parts soy bean oil and 1 pa China-Wood oil.

A mixture of 2 parts cashew nut shell'oil and 1 part China-wood oil.

Norwegian cod liver 011.

Light menhaden fish oil.

China-wood oil.

Example 5 Dehydrated castor oil (gelatinizing temperature of 300 C. used). (b) Synthetic drying oil (gelatinizing temperature of about 270 C. used) (Nee-fat). (0) Synthetic oil (gelatinizing temperature of about 280 C. used) (Trlmol") Example 6 100 parts commercial refined, bodied linseed oil was mixed with 8-10 parts commercial t-butyl-hydro-peroxide and heated. At around 150 C., strong gas formation occurred and gelatinization took place between 200 and 230 C.; that is, considerably below the gelatinization temperature of raw linseed oil. The gel was light in color.

Example 7 Gelatinized oils were also obtained by distilling oil the non-gelatinizing portions of various oils. This was accomplished under diminished pressure by continuing the distillation at about or slightly above 270 C. until the desired degree of gelatinization occurred.

. a l 7 Example 8 A gelatinized oil was obtained by chemical action by, heating 40 grams linseed oil to a temperature of about 50 to 100 C. About one part of boron trifluoride gas was added to the oil under stirring until gelatinization occurred. The mixing of the boron trifluoride with oil also was accomplished at a lower temperature and the mixture then heated so that an at least partially insoluble gel condition was obtained. The el was washed with water for removal of the Water soluble products.

(a) In a further example, 3 arts of a mixture of 1 part boron trifluoride e herate with 2 parts solvent was added in place of the boron trifluoride gas.

Example 9 45 parts of linseed oil were mixed with 10 to 20 parts of tetra-chloro-phthalic-anhydride; The mixture was heated to about 200 C. until gel forming began. 20 more parts of oil were added and heating was continued'until an at least partially insoluble oleo-gel had been formed.

The material was then washed with water for removing watersoluble products.

Example 10 In the following examples, oil-modified alkyd resins (commercial combinations of oils or oilacids with reaction products of phthaliclanhydride and glycerols) were gelatinized according to the process set forth in Example 3.

SOLUBILIZING THE SWELL-ED, INSOLUBLE, GELATINOUS Frxnn OIL BASE Example 11 40 parts by weight of the insoluble gelatinous linseed oil base made in accordance with the process set forth in Example 3 above was melted together with about 10 parts by weight of the metal soap-like reaction product obtained in accordance with the process set forth in Example 1. The melting temperature of the swelled insol-- uble gelatinous linseed oil base varies in accordance with its condition and age. However, it has been found that an average temperature of about 250 C. may be used as a melting temperature. Melting is complete when the composition has become uniform throughout. The resulting product is in the form of a stable, soluble, linseed oil base composition having a high shrinkage capacity when dried from a state of solution. The resulting composition may be stored with great resistance to aging and it may be thinned with 7 various quantities and various types of solvents or mixtures of solvents. In this condition it may be combined with natural or synthetic resins. asphalts, copal gums or solutions thereof. In addition, it may be readily melted with either natural or synthetic resins, asphalts, or cons] gums.

While preferred heating temperatures for the treating, compounding, .and gelatlnizing have been set forth in the foregoing examples, it will be understood that temperatures will vary in Gelntinieed oil Contact substance 20 parts China-wood oil-gel 39 parts China-wood oil-gel 20 puts perilla oil-r l 20 parts soy bean oil-gel 20 parts gel from 4 parts China-wood oil, 15 parts soy bean oll 20 parts perilla oil-gel 20 parts cod liver oil-gel 2) parts light menhaden fish oil-gel 20 parts gelatinized dehydrated castor oil 20 parts gelatinioed synthetic drying oil 20 parts gelatinized synthetic oil.

20 parts light colored gelatinized linseed oil obtained irom reacting 105 parts linseed oil and 8-10 parts t-butyLhydroperoxide at about 200235 C.

20 parts light colored gelatinized linseed oil obtained from reacting 105 parts linseed oil and 840 parts t-butyl-hydroperoxide at about 200-235" C.

61 parts linseed oil-gel 20 parts gelatinized linseed obtained by diminished pressure 20 parts gelatinized perilla oil obtained by distillation under diminished pressure.

20 parts gelatinized cottonseed oil obtained by distillation under jugated linseed oil and 1 part cottonseed oil. 7

10 parts obtained from reacting 93 parts linseed oil and 4 parts lead acetate.

7 parts obtained: from reacting 77.5 parts linseed oil, 15.5 parts oleic acid and 1.5 parts cobalt acetate.

5 parts obtained. from reacting 77.5 parts linseed oil, 15.5 parts resin acid and 2 parts cobalt acetate.

5 parts obtained irom reacting 93 parts perilia oil and 02.2 parts cnpric oxalate.

6.2 parts obtained from reacting 93 parts perilla oil and 11.2

parts zinc sulfate.

5 parts obtained irom reacting 93 parts cottonseed oil and 7.7

parts cobaltous nitrate.

6 parts obtained from reacting 93 parts cashew nut shell oil and 4.8 ts cobalt acetate.

5.5 ta tained from reacting 93 parts light menhaden ilsh oi and 12.4 parts nickel iormiate.

parts obtained from reacting 93 parts modified (dehydrated) castor oil and 2.8 parts cobalt acetate.

6 parts obtained from reacting 37 parts linseed oil. 46 parts rosin oil, and 2 arts cobalt acetate.

5.5 ports obtains from reacting 93 parts linoleic acid and 2.15

parts bismuth acetate (basic).

5.5 parts obtained irom reacting 93 parts linoleic acid and 2.4

parts chromium carbonate.

5.5 parts obtained from reacting 70 parts linseed oil, 23 parts naphthenic acid and 2.4 parts cobalt acetate.

7.5 parts obtained irom reacting 70 parts linseed oil, 23 parts stearic acid and 2.35 parts bismuth acetate (basic).

6 parts obtained irom reacting 93 parts linoleic acid and 2.8

parts manganese acetate.

0 parts obtained from reacting,93 parts resin acids in the form oi rosin oil and 2.35 parts co alt acetate.

5.6 parts obtained irom reacting 93 parts naphthenic acids and 2.8 parts cobalt acetate.

parts obtained irom reacting 93 parts China-wood oil and 5 parts cobalt acetate.

20 parts dibutyi tin dilaureate and parts naphthenic acid.

5.6 parts obtained from reacting 93 parts perilla oil and 9.3 parts si ver nitrate.

10 parts obtained irom reacting 93 parts soy bean oil and 4.2

parts cobalt acetate.

10 parts obtained from reacting 93 parts linseed oil and 1.5 parts cobalt acetate.

3 parts obtained irom reacting 93 parts perilla oil and 9.3 parts silver nitrate.

2 parts obtained irom reacting 93 parts linseed oil and 1.5 parts cobalt acetate.

10 parts obtained irom reacting 93 parts linseed oil and 1.5 parts cobalt acetate.

7.2 parts obtained from reacting 93 parts cod liver oil and 3.1

parts lead acetate.

8 parts obtained from reacting 93 parts dehydrated castor oil and 2.8 parts cobalt acetate.

10 parts obtained from reacting 93 parts linseed oil and 1.5 parts cobalt acetate.

11 parts obtained from reacting 93 parts synthetic drying oil and 3.5 parts cobalt acetate.

10 parts obtained from reacting 93 parts synthetic oil and 4.6

parts cobalt acetate.

6 parts obtained from reacting 93 parts linseed oil and 1.5 parts cobalt acetate.

10 arts obtained from reacting 93 parts linseed oil and 3.1 parts 0 romium carbonate.

26 parts obtained from reacting 93 parts linseed oil and 13 parts ZnO: (55%).

8 parts obtained from reacting 93 parts linseed oil and 1.5 parts cobalt aceta 6.1 parts obtained irom reacting 62 parts perilla oil, 31 parts distillate oi perilla oil and 4.5 parts cobalt acetate.

10 parts obtained from reacting 93 parts distillate oi cottonseed oil and 6 parts cobalt acetate.

14 parts obtained irom reacting 93 parts dehydrated castor oil and 2.8 pmts cobalt acetate.

13.3 parts obtained from reacting 93 parts dehydrated castor oil and 2.8 parts cobalt acetate.

10 parts obtained from reacting 10 parts linseed oil, 2 parts oleic acid and 0.2 part cobalt acetate.

10 parts obtained from reacting 93 parts linseed oil and 1.5

parts cobalt acetate.

accordance with the physical condition, age, and types of compositions employed.

The process set forth in Example 11 was followed in solubilizing the insolubilized oils of Example 3 with the soap-like reaction products of Examples 1-2. The fixed oil reaction products in accordance with the following examples readily Example 12 Example 13 This exemplifies the process of Example 11, as applied to commercial gels derived from vegetable, animal or synthetic oils (including those derived from mineral oils) or mixtures, containing the same and using any of the contact materials made according to Example 1 and 2.

parts commercial linseed oil gel containing 15% volatile matter.

8 parts contact material obtained from reacting 93 parts linseed oil and 1.5 parts cobalt acetate 11 temple 14 asraevo Emmple 17 This exemplifies the process of Example 11 as I applied to the gels produced in Example 10 from commercial alkyd resins:-

Gel

Contact substance Added Compound 20 parts gel of ExamplelOb.

c 20partsgel oi'Example 10c-..

mparts lot Exam lelOa..- 10 parts obtained from 98 parts llnseedoll 2.1 parts bodied non-gelatlnized n p d tats linseed ii an 1.5 gens cobalt ace 16.5 parts tained from 93 parts dehydrated mstor oil and 2.8 parts cobalt acetate.

parts obtained from 93 parts linseed oil and 1.5 parts cobalt acetate.

o 3.5 parts dehydrated castor oil.

2 parts bodied non-gelatlnioed linseed oil.

liquid at the solubilizing reaction temperature, (2) a solvent for the contact substance and (3) a swelling agent for the gelatinous material. In this manner, heavy-bodied gels and heavy-bodied contact substances may be obtained.

The resulting reaction products were thinned with an equal part of toluene and clear stable solutions were obtained. Each 01' these solutions was mixed with an equal amount or the Oil-gel Contact substance Added Compound t h linseed oil el 10 arts obtained from 98 parts linseed oil and 5.5 parts basis a 20 par 8 a? g a luminum acetate (a nearly solid reaction product).

6.6 parts obtained from 93 parts linseed oil and l .5 parts cobalt acetate. 20 parts obtained from 96 parts dehydrated castor oil and c. 20 parts heavy gel obtained'irom 20 parts cashew nut shell and 2.8 parts cobalt acetate.

nous pe a oil. 10 parts dehydrated castor oil.

1 t Chin wood oil. 1... 20 p r t s obtain zd irom conju- 11 parts obtained from 93 parts dehydrated castor oil and 4 parts conjugated liniugated linseed oil. 2.8 parts cobalt acetate. seed oil,

Example 15 non-gelatinized starting material and clear stable,

This exemplifies the process of Example 11 as applied to gelatinous oil products obtained by chemical action like those produced in Examples 8 and 9 using the contact substances set forth in Examples 1 and 2.

soluble products were obtained. Example 18 The process set forth in Example 11 was modifled by adding during, and/or after, the process of liquifying the gel, an amount or natural res ns.

Added Oil-Gel Contact substance Compound 20 a is linseed oil reduced 32 arts of a mixture containing e uui parts oi a reaction product 3.2 its linth boron trifluorid etherate c tained from 93 parts linseed oil and 1.5 parts cobalt acetate, and se d oil.

(Sec Example 8). from 93 parts oleic acid and 20 parts zinc benzocte. b 20 parts linseed oil gel produced 20 parts obtained from 93 parts linseed oil and 1.5 parts cobalt aoetate 2.4 parts linwith tetrachlorophthalic anhyseed oil. dride (Bee Example 9).

Emmple 16 gums. asphalts, oils and dryers by melting them This exemplifies the process set forth in Examtogether. 1

Solubilized Reaction Product Added Compound a 508mm solubilized reaction product obtained from process of Example 11 parts asphalt.

wiarts linseed oil gel plus 10 parts contact substance from 98 parts lin.

1 see oil andl.5 parts cobalt acetate).

12 parts of solubilized reaction product obtained from process of Example 11 (40 parts linseed oil gel plus 10 parts contact substance from 93 parts linseed oil and 1.5 parts cobalt acetate).

40 parts ester gum, 10 parts lead manganese resinatc, 0.5 port cobait naphthenate dryer.

ple 11, as applied to oleo-gels, known as vulcanized oils" or as factice materials or as rubber substitutes obtained by the efiect of sulphur ("brown material) or sulphur chlorides ("white material) or other vulcanizing agents (e. g. "amber" material), using any of the contact materials made in accordance with Examples 1 and 2. It was noted that in an accompanying secondary reaction, a sedimentation of metal sulphides occurred frequently and became visible, particularly in the thinned solution. The sedimentation was separated by usual methods and did not interfere with the solubilizing itseli'.

The final products were thinned with an equal amount 01 petrol naphtha and formed a stable Example 19 The process of Example 18 was practiced wherein a phenol-formaldehyde synthetic resinous' material was added. The final product was dissolved in an equal volume of toluene and formed a stable solution.

It also has been found that the solubilized final reaction product may be modified by the addition 01' a gelatinized material and then heating the mixture until gelatinization re-occurs.

Vulcanized on Product Contact Substance 10 parts obtained irom reacting 93 parts olcic acid and w btiiflh i ting as parts lei acid ii 0 rom rose 0 c an parts zinc benzoate c 20 parts sulphur vulcanized soybean oil parts obtained from reacting 98 parts dehydrated oleo-materlal.

. castor oil and 2.8 parts cobalt acetate. d. 20 parts amber colored chlorinefree commercial vulcanized 20 parts obtained f I 20 parts lead hydroxide.

. Example 20 V 50 parts of the solubllized final reaction product of Example 11 were heated with 50 parts of China-wood oil to about 300 C. A partially insoluble gelatinized final product was obtained.

Example 20a Example 20b 1 i 100 parts of the solubilized final reaction prodnot of Example 11 were slowly heated with parts lamoyl peroxide to a gelatinizing temperature of about 120 C. at which point the product again became an insoluble, gelatinous mass.

Example 21 60 parts solidified alkyd resin (containing about 15 parts polyhydroxyl alcohol, 35 parts phthalic anhydride and 50 parts soy bean oil ingredients) were compounded at a melting temperature of 250 C. with 40 parts reaction product (containing 37% lead) obtained from reacting naphthenic acid and lead acetate.

One part each of the final reaction product produced a clear, stable solution when dissolved in (1) 2 parts non-gelatinized linseed oil; (2) one part toluene; (3) one part mono-styrene; (4) a solution of one part mono-styrene in one part toluene.

In addition, it has been found that the solubilization of the insoluble gelatinized oils may be accomplished with the contactsubstances in the presence of other materials such as asphalt, nongelatinized oils, resins, gums, synthetic resinous materials, such as phenolic resins and alkyd resins.

In accordance with the foregoing examples, it will be understood that the metals of the salts. oxides, peroxides, hydroxides, carbonates, ace tates, etc., are not limited to any one group of the periodic system.

It further will be understood that fillers, pigments, etc., may be utilized to modify products of the present invention so that they may be used in the coating and impregnating arts.

It further will be understood that the melting temperature employed to solubilize the insoluble oils by compounding therewith a metal soap-like reactionproduct is such that substantially the entire mass of the resulting composition is melted into the liquid stage. In this respect the melting temperature of the present invention is distinguished from the use of a lower temperature which is incapable of melting substantially the entire mass into a liquid state. By use of above specified melting temperature it is possible to form a soluble reaction product which is capable of forming a stable solution; whereas this is not possible when a temperature below' the melting temperature is employed. Moreover, the solubilized final reaction product, obtained by employing a melting temperature, is capable of being heated without gelatinizing and is further capable of being regelatinized as set forth in Example 20 and 20a. Moreover, the regelatinprocess of the present invention.

Coatings, impregnations, coverings, extrusions and compoundings made from the oil base coat- .ing compositions of the present invention, possess great elasticity and great resistance to aging, hardening, changes in temperature and humidity and are thereby particularly adapted for the production of coatings, such as varnishes and the like.

The oil base coating compositions of the present invention may be melted with natural or synthetic resins, asphalts, copal gums and the like so as to alter their physical properties, such as to increase hardness, lower elasticity, or for changing color eflect, acid resistance, drying conditions and the like. Coatings and impregnations obtained from the oil base coating compositions of the present invention may be further hardened or solidified either during or after drying by the use of vulcanizing or accelerating agents.

In addition, the compositions of the present invention may also be used as plasticizers for resinous compounds, cellulose lacquers, plastic compounds and the like.

Coatings and impregnations made from the oil base coating compositions of the present invention may be dried with or without the application of heat, or drying may be accelerated by the action of polymerization accelerators such as sulphur chlorides, tin tetrachlorides, organic peroxides and the like.

The oil base coating compositions of the present invention may be used for the preparation of oil compounds, varnishes, lacquers, coatings, extrusions, coverings, for the modification of resinous materials, and as impregnations for cloth and the like. In addition, they may be used for producing electrical insulating materials, such as binding materials for fiber windings. They may also be used as heat and moisture insulating materials and as laminating compounds' I claim:

1. A method of solubilizing an at least partially with said oil a compound comprising a metal soap of a compound selected from the group consisting of higher fatty acids, higher fatty acid esters, petroleum acids and, rosin acids, at a melting temperature below the decomposition temperature of the resulting composition and at such melting temperature that substantially the entire mass of the resulting composition is melted into the liquid stage, whereby to form a soluble fixed oil reaction product which is capable of forming a stable solution.

2. The process set forth in claim 1, wherein the at least partially insoluble and at least partially gelled oil is derived from a vegetable oil.

3. The process set forth in claim 1, wherein the at least partially insoluble and at least partially gelled oil is derived from an animal oil.

4. The process set forth in claim 1, wherein the at least partially insoluble and at least partially gelled oil is derived from a synthetically produced oil-like ester of a higher fatty acid.

5. A method of solubilizing an at least partially insoluble and at least partially gelled linseed oil which comprises melting and compounding with said oil a compound comprising a metal soap of a compound selected from the group consisting of higher fatty acids, higher fatty-acid esters, petroleum acids and rosin acids, at a melting temmore perature below the decomposition temperature Q of the resulting composition and at such melting temperature that substantially the entire mass of the resulting composition is melted into the liquid stage, whereby to form a soluble linseed oil reaction product which is capable of forming a stable solution.

6. A method of solubilizing an at leastpartially insoluble and at least partially gelled China-wood oil which comprises melting and compounding with said oil a compound comprising a metal soap of a compound selected from the ground consisting of higher fatty acids, higher fatty acid esters, petroleum acids and rosin acids, at a melting temperature below the decomposition temperature of the resulting composition and at such meltin temperature that substantially the entire mass of the resulting composition is 1 melted into the liquid stage,

.whereby to form a soluble China-wood oil reaction product which is capable of forming a stable solution. I

7. A method of solubilizing anat least partially insoluble and at least partially gelled soy bean oil which comprises melting and compounding with said oil a compound comprising a metal soap of a compound selected from the group consisting of higher fatty acids, higher fatty acid esters, petroleum acids and rosin acids, at a melting temperature below the decomposition temperature of the resulting composition and at such melting temperature that substantially the entire mass of the resulting composition is melted into the liquid stage, whereby to form a soluble soy bean oil reaction product which is capable of forming a stable solution.

8. A method of solubilizing an at least partially insoluble and at least partially gelled composition comprising a synthetically produced 011- like ester of a higher fatty acid and a polyhydric alcohol having not more than 6 OH groups, which comprises melting and compounding with said composition a compound selected from the group consisting of higher fatty acids, higher fatty acid esters, petroleum acids and rosin acids, at a melting temperature below the decomposition temperature of the resulting composition and at such melting temperature that substantially the entire mass of the resulting composition is melted into the liquid stage, whereby to form a soluble reaction product which is capable of forming a stable solution. v 9. A method of solubilizing an at least partially insoluble and at least partially gelled composition comprising a synthetically produced oillike ester of a higher fatty acid and a polyhydric alcohol having not more than 6 OH groups and an esterforming acid, which-comprises melting and compounding with said composition a compound comprising a metal soap of a compound selected from the group consisting of higher fatty acids, higher fatty acid esters, petroleum acids and rosin acids at a melting temperature below' the decomposition temperature of the resulting composition and at such melting temperature that substantially the entire mass of the resulting composition is melted into the liquid stage, whereby to form a soluble reaction product which is capable of forming a stable solution. 10. A method of solubilizing an at least partially insoluble and at least partially gelled composition comprising a synthetically produced oillike ester of a higher fatty acid and a 'polyhydric alcohol having not more than .6 OH groups and phthalic anhydride, which comprises melting and 1'6 compounding said composition, a compound comprising a metal soap of a compound selected from the group consisting of higher fatty acids. higher fatty acid esters, petroleum acids and rosin acids at a melting temperature'below the decomposition temperature .of the resulting composition and at such melting temperature that substan tially the entire mass of the resulting composi-- tion is melted into the liquid stage, whereby to form a soluble reaction product which-is capable of forming a stable solution. a

11. A method of solubilizing an at least par tially insoluble and at least partially gelled oil selected from the group consisting of fixed oils and a synthetically produced oil-like ester of a higher fatty acid which comprises melting and compounding with said oil a compound comprising a metal soap of a higher fatty acid substance, at a melting temperature below the decomposition temperature of the resulting composition and at such melting temperature that substantially the entire mass of the resulting composition is melted into the liquid stage, whereby to form a soluble fixed oil reaction product which is capable of forming a stable solution.

12. A method of solublizing an at least partially insoluble and at least partially gelled oil selectedfrom the group consisting of fixed oils and a synthetically produced oil-like ester of a higher fatty acid which comprises melting and compounding with said oil a compound comprising a metal. soap of a petroleum acid, at a melting temperature below the decomposition temperature of the resulting compositionand at such melting temperature that substantially the entire mass of the resulting composition is melted into the liquid stage, whereby to form a solluble fixed oil reaction product which is capable of forming a stable solution.

13. A method Of SOlllbfliZlllg an at least partially insoluble and at least partially gelled oil selected from the group consisting of fixed oils and a synthetically produced oil-like ester of acapable of forming a stable solution.

14. A method or solubilizing an at least par-.

tially insoluble and at least partially gelled oil selected from the group consisting of fixed oils and a synthetically produced oil-like ester of a higher fatty acid which comprises melting and compounding with said oil. a compound comprising a metal soap of a naphthenic acid, at a melting-temperatur below the decomposition temperature of the resulting composition and at such melting temperature that substantially the entire mass of the resultingicomposition is melted into the liquid stage, whereby to form a soluble fixed oil reaction product which is capable of forming a stable solution. g

15. A soluble, stable oil composition comprising the reaction product of an at least partially insoluble and at least partially gelled oil selected from the group consisting of fixed. oils and a synthetically, produced oil-like ester of a higher fatty acid with a compound comprising a metal soap of a compound selected from the group consisting of higher fatty acids, higher fatty acid 2,470,131 17 18 esterzedpeig-olemnflgclt and trout}, eddsthcocm- REFERENCES CITED poun a. ame g mperaure eow e ecomposition temperature of the resulting comfi m g are of record in the position and at such melting temperature that e 0 pa substantially the entire mass of the resulting FOREIGN PATENTS com m is elted intoth 11 1d t pm on m ufix im wm. Cmmtry Date 1,388 Great Britain 1901 

